Coated pipe with high throughput using multimodal ethylene copolymer

ABSTRACT

The present invention deals with coated pipes having a layer of multimodal polyethylene. The multimodal ethylene copolymer is a copolymer of ethylene with one or more alpha-olefin comonomers having from 4 to 10 carbon atoms and has a weight average molecular weight of from 70000 g/mol to 250000 g/mol, the ratio of the weight average molecular weight to the number average molecular weight, Mw/Mn, of from 15 to 50, a melt index MFR 2  of from 0.05 g/10 min to 5 g/10 min, a melt index MFR 5  of from 0.5 to 10 g/10 min and a density of from 930 kg/m to 955 kg/m 3 . Further, the multimodal ethylene copolymer comprises the multimodal ethylene copolymer comprises from 49 to 59% based on the weight of the multimodal ethylene copolymer a low molecular weight ethylene homopolymer component, said low molecular weight ethylene homopolymer having a weight average molecular weight of from 5000 g/mol to 70000 g/mol; and from 51 to 41% based on the weight of the multimodal ethylene copolymer a high molecular weight ethylene copolymer component, said high molecular weight ethylene copolymer having a weight average molecular weight of from 100000 g/mol to 700000 g/mol. The pipes can be coated with high throughput and good production economy. The coatings have good mechanical properties.

OBJECTIVE OF THE INVENTION

The present invention is directed to polymer coated pipes. More specifically, the present invention is directed to coated metal pipes having a high mechanical strength and which can be produced at a high throughput. In addition, the present invention is directed to a method of producing such coated metal pipes with a high throughput and good production economy.

TECHNICAL BACKGROUND AND PRIOR ART

The use of bimodal or multimodal ethylene polymers in coating of steel pipes is known from EP-A-837915. However, even though the document teaches that the composition has a good processability it still remains a wish to further improve the processability, like maximum throughput and neck-in behaviour.

SUMMARY OF THE INVENTION

The present invention provides polyethylene coated metal pipes that have an improved resistance against stress cracking and/or can be used at high service temperature. The pipes according to the present invention comprise an inner surface and an outer surface layer (A) and a coating layer (B) covering said outer layer (A), wherein

the coating layer (B) comprises a coating composition (B-2) comprising a multimodal copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms (B-1), wherein the multimodal ethylene copolymer (B-1) further comprises

(B-1-1) from 49 to 59% based on the weight of the multimodal ethylene copolymer (B-1) of a low molecular weight ethylene homopolymer component, said low molecular weight ethylene homopolymer having a weight average molecular weight of from 5000 g/mol to 70000 g/mol; and

(B-1-2) from 51 to 41% based on the weight of the multimodal ethylene copolymer (B-1) of a high molecular weight ethylene copolymer component, said high molecular weight ethylene copolymer having a weight average molecular weight of from 100000 g/mol to 700000 g/mol; and

the multimodal ethylene copolymer has a weight average molecular weight of from 70000 g/mol to 250000 g/mol and a melt index MFR₂ of from 0.05 g/10 min to 5 g/10 min, preferably from 0.1 to 1.2 g/10 min and more preferably 0.2-0.8. Preferably, it further has an MFR₅ of 0.5 to 10 g/10 min, more preferably from 1.0 to 5.0 g/10 min. Preferably still it has a density of from 930 kg/m³ to 955 kg/m³.

The present invention also provides a method for producing the coated pipes as disclosed above. The process comprises the steps of:

providing a pipe having an outer surface layer (A);

applying a coating layer (B) onto the pipe outer layer (A), wherein the coating layer (B) comprises a coating composition (B-2) comprising a multimodal copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms (B-1), wherein the multimodal ethylene copolymer (B-1) further comprises

(1) from 49 to 59% based on the weight of the multimodal ethylene copolymer (B-1) a low molecular weight ethylene homopolymer component (B-1-1), said low molecular weight ethylene homopolymer (B-1-1) having a weight average molecular weight of from 5000 g/mol to 70000 g/mol; and

(2) from 51 to 41% based on the weight of the multimodal ethylene copolymer (B-1) a high molecular weight ethylene copolymer component (B-1-2), said high molecular weight ethylene copolymer (B-1-2) having a weight average molecular weight of from 200000 g/mol to 700000 g/mol and a content of alpha-olefin comonomer units of from 0.5 to 10% by mol, based on the total amount of repeating units in the high molecular weight ethylene copolymer component (B-1-2); and

the multimodal ethylene copolymer (B-1) has a weight average molecular weight of from 70000 g/mol to 250000 g/mol and a melt index MFR₂ of from 0.05 g/10 min to 5 g/10 min and a density of from 930 kg/m³ to 955 kg/m³.

As seen from another aspect, the invention provides a process comprising the steps of:

(i) polymerising, in a first polymerisation stage, a low molecular weight ethylene homopolymer in the presence of a polymerisation catalyst, hydrogen, ethylene and optionally an inert diluent to produce an ethylene homopolymer having a weight average molecular weight of from 5000 g/mol to 70000 g/mol which constitutes from 49 to 59% by weight of the multimodal ethylene copolymer (B-1); and

(ii) polymerising, in a second polymerisation stage, a high molecular weight copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms in the presence of a polymerisation catalyst, ethylene, at least one alpha-olefin comonomer having from 4 to 10 carbon atoms, and optionally hydrogen and/or an inert diluent to produce a copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms having a weight average molecular weight of from 200000 g/mol to 700000 g/mol, which high molecular weight ethylene component constitutes from 41 to 51% by weight of the multimodal ethylene copolymer (B-1); and wherein said first and said second polymerisation step are performed as successive polymerisation steps with the polymer product produced in any previous step being present in the subsequent step(s) and wherein said first step and said second step can be performed in any order and wherein the resulting multimodal ethylene copolymer (B-1) has a weight average molecular weight of from 70000 g/mol to 250000 g/mol and a melt index MFR₂ of from 0.05 g/10 min to 5 g/10 min, a melt index MFR₅ of from 0.5 to 10 g/10 min and a density of from 930 kg/m³ to 955 kg/m³;

(iii) recovering said multimodal ethylene copolymer (B-1);

(iv) obtaining the coating composition (B-2) comprising 80 to 100% by weight, preferably from 85 to 100% by weight and in particular from 90 to 99% by weight of the multimodal ethylene copolymer (B-1), optional additives and optional other polymers;

(iv) applying said coating composition (B-2) onto the pipe outer layer (A) to form the coating layer (B).

Using the coating composition according to the present invention coated pipes with good mechanical properties can be produced with improved throughput and good process economy. Further, the coated pipes have a smooth surface.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a sample with a notch used to determine the constant tensile load of a coating composition of the invention.

DETAILED DESCRIPTION

Multimodal Ethylene Copolymer

The multimodal ethylene copolymer (B-1) comprises a low molecular weight ethylene homopolymer component and a high molecular weight ethylene copolymer component. The multimodal ethylene copolymer (B-1) has a weight average molecular weight of 70000 to 250000 g/mol, a melt index MFR₂ of from 0.05 to 5 g/10 min, preferably from 0.1 to 1.2 g/10 min, and more preferably from 0.2 to 1.0 g/10 min. Preferably, it further has an MFR₅ of 0.5 to 10 g/10 min, more preferably from 1.0 to 5.0 g/10 min. Furthermore, the multimodal ethylene copolymer (B-1) has a density of from 930 to 955 kg/m³, preferably from 935 to 955 kg/m³ and more preferably from 935 to 953 kg/m³.

Preferably the multimodal ethylene copolymer (B-1) has a broad molecular weight distribution as indicated by the ratio of weight average molecular weight to the number average molecular weight, Mw/Mn, of from 20 to 50, preferably from 24 to 50 and in particular from 25 to 40.

The multimodal ethylene copolymer (B-1) comprises from 49 to 59% by weight, based on the multimodal ethylene copolymer (B-1), of low molecular weight ethylene homopolymer component (B-1-1). The low molecular weight ethylene homopolymer component (B-1-1) has a weight average molecular weight of from 5000 to 70000 g/mol, preferably form 15000 to 50000 g/mol. Preferably the low molecular weight ethylene homopolymer component (B-1-1) has a melt index MFR₂ of from 100 to 1500 g/10 min, more preferably from 150 to 1000 g/10 min.

The inventors have found that when the amount of the low molecular weight ethylene homopolymer fraction is within the specified limits the processability of the coating composition is improved. Usually also the resulting multimodal ethylene copolymer (B-1) then has a broad molecular weight distribution and a high tendency for shear thinning, as indicated by a high value of the shear thinning index. Furthermore, smooth coatings without surface defects are obtained.

It should be understood that within the meaning of the present invention the term “homopolymer” is used to mean a linear ethylene polymer which essentially consists of ethylene repeating units. It may contain trace amount of units derived from other polymerisable monomers, but it should contain at least about 99.9% by mole of ethylene repeating units, based on all the repeating units present in the low molecular weight ethylene homopolymer component (B-1-1).

The multimodal ethylene copolymer (B-1) also comprises from 41 to 51% by weight, based on the multimodal ethylene copolymer (B-1), a high molecular weight copolymer of ethylene and alpha-olefins having from 4 to 10 carbon atoms (B-1-2). The high molecular weight copolymer component (B-1-2) has a weight average molecular weight of from 100000 to 700000 g/mol, preferably 150000 to 300000 g/mol. Preferably it further has a content of alpha-olefin comonomers having from 4 to 10 carbon atoms of 0.5 to 10% by mole, in particular from 1 to 5% by mole, based on the total number of moles of repeating units in the high molecular weight copolymer component (B-1-2).

It should be understood that within the meaning of the present invention the term “copolymer of ethylene and alpha-olefins having from 4 to 10 carbon atoms” is used to mean an ethylene polymer which essentially consists of ethylene repeating units and repeating units derived from alpha-olefins having from 4 to 10 carbon atoms. It may contain trace amount of units derived from other polymerisable monomers, but it should contain at least about 99.9% by mole of above-mentioned repeating units, based on all the repeating units present in the high molecular weight ethylene copolymer component (B-1-2).

In addition to the two components referred above the multimodal ethylene copolymer (B-1) may contain up to 10% by weight of other polymer components. The amount and the properties of such additional polymer components may be selected freely provided that the properties of the multimodal ethylene copolymer and of the two above-mentioned components are those discussed above.

Polymerisation Process

The multimodal ethylene copolymer may be produced in any suitable polymerisation process known in the art. Preferably the multimodal ethylene copolymer is produced in a sequential polymerisation process comprising at least two polymerisation zones operating at different conditions to produce the multimodal copolymer. The polymerisation zones may operate in slurry, solution, or gas phase conditions or their combinations. Suitable processes are disclosed, among others, in WO-A-92/12182 and WO-A-96/18662.

Catalyst

The polymerisation is conducted in the presence of an olefin polymerisation catalyst. The catalyst may be any catalyst which is capable of producing all components of the multimodal ethylene copolymer. Suitable catalysts are, among others, Ziegler-Natta catalysts based on a transition metal, such as titanium, zirconium and/or vanadium or metallocene catalysts or late transition metal catalysts, as well as their mixtures. Especially Ziegler-Natta catalysts and metallocene catalysts are useful as they can produce polymers within a wide range of molecular weight with a high productivity.

Suitable Ziegler-Natta catalysts preferably contain a magnesium compound, an aluminium compound and a titanium compound supported on a particulate support.

The particulate support can be an inorganic oxide support, such as silica, alumina, titania, silica-alumina and silica-titania. Preferably, the support is silica.

The average particle size of the silica support can be typically from 10 to 100 μm. However, it has turned out that special advantages can be obtained if the support has an average particle size from 15 to 30 μm, preferably from 18 to 25 μm. Alternatively, the support may have an average particle size of from 30 a 80 μm, preferably from 30 to 50 μm. Examples of suitable support materials are, for instance, ES747JR produced and marketed by Ineos Silicas (former Crossfield), and SP9-491, produced and marketed by Grace.

The magnesium compound is a reaction product of a magnesium dialkyl and an alcohol. The alcohol is a linear or branched aliphatic monoalcohol. Preferably, the alcohol has from 6 to 16 carbon atoms. Branched alcohols are especially preferred, and 2-ethyl-1-hexanol is one example of the preferred alcohols. The magnesium dialkyl may be any compound of magnesium bonding to two alkyl groups, which may be the same or different. Butyl-octyl magnesium is one example of the preferred magnesium dialkyls.

The aluminium compound is chlorine containing aluminium alkyl. Especially preferred compounds are aluminium alkyl dichlorides and aluminium alkyl sesquichlorides.

The titanium compound is a halogen containing titanium compound, preferably chlorine containing titanium compound. Especially preferred titanium compound is titanium tetrachloride.

The catalyst can be prepared by sequentially contacting the carrier with the above mentioned compounds, as described in EP-A-688794 or WO-A-99/51646. Alternatively, it can be prepared by first preparing a solution from the components and then contacting the solution with a carrier, as described in WO-A-01/55230.

Another, especially preferred, group of suitable Ziegler-Natta catalysts contain a titanium compound together with a magnesium halide compound without an inert support. Thus, the catalyst contains a titanium compound on a magnesium dihalide, like magnesium dichloride. Such catalysts are disclosed, for instance, in WO-A-2005/118655 and EP-A-810235.

The Ziegler-Natta catalyst is used together with an activator. Suitable activators are metal alkyl compounds and especially aluminium alkyl compounds. These compounds include alkyl aluminium halides, such as ethylaluminium dichloride, diethylaluminium chloride, ethylaluminium sesquichloride, dimethylaluminium chloride and the like. They also include trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium, trihexylaluminium and tri-n-octylaluminium. Furthermore they include alkylaluminium oxy-compounds, such as methylaluminiumoxane, hexaisobutylaluminiumoxane and tetraisobutylaluminiumoxane. Also other aluminium alkyl compounds, such as isoprenylaluminium, may be used. Especially preferred activators are trialkylaluminiums, of which triethylaluminium, trimethylaluminium and tri-isobutylaluminium are particularly used.

The amount in which the activator is used depends on the specific catalyst and activator. Typically triethylaluminium is used in such amount that the molar ratio of aluminium to the transition metal, like Al/Ti, is from 1 to 1000, preferably from 3 to 100 and in particular from about 5 to about 30 mol/mol.

As discussed above, also metallocene catalysts may be used to produce the multimodal ethylene copolymer. Suitable metallocene catalysts are known in the art and are disclosed, among others, in WO-A-95/12622, WO-A-96/32423, WO-A-97/28170, WO-A-98/32776, WO-A-99/61489, WO-A-03/010208, WO-A-03/051934, WO-A-03/051514, WO-A-2004/085499, EP-A-1752462 and EP-A-1739103.

Polymerisation

The polymerisation zone where the low molecular weight ethylene homopolymer (B-1-1) is produced typically operates at a temperature of from 20 to 150° C., preferably from 50 to 110° C. and more preferably from 60 to 100° C. The polymerisation may be conducted in slurry, gas phase or solution.

The catalyst may be transferred into the polymerisation zone by any means known in the art. It is thus possible to suspend the catalyst in a diluent and maintain it as homogeneous slurry. Especially preferred it is to use oil having a viscosity form 20 to 1500 mPa·s as diluent, as disclosed in WO-A-2006/063771, it is also possible to mix the catalyst with a viscous mixture of grease and oil and feed the resultant paste into the polymerisation zone. Further still, it is possible to let the catalyst settle and introduce portions of thus obtained catalyst mud into the polymerisation zone in a manner disclosed, for instance, in EP-A-428054. The polymerisation zone may also be preceded by a prepolymerisation zone, in which case the mixture withdrawn from the prepolymerisation zone is directed into the polymerisation zone.

Into the polymerisation zone is also introduced ethylene, optionally an inert diluent, and optionally hydrogen and/or comonomer. The low molecular weight ethylene homopolymer component (B-1-1) is produced in a first polymerisation zone and the high molecular weight ethylene copolymer component (B-1-2) is produced in a second polymerisation zone. The first polymerisation zone and the second polymerization zone may be connected in any order, i.e. the first polymerisation zone may precede the second polymerisation zone, or the second polymerisation zone may precede the first polymerisation zone or, alternatively, polymerisation zones may be connected in parallel. However, it is preferred to operate the polymerisation zones in cascaded mode.

As it was disclosed above, the low molecular weight homopolymer (B-1-1) is produced in the first polymerisation zone. Into the first polymerisation zone are introduced ethylene, hydrogen and optionally an inert diluent. Comonomer is not introduced into the first polymerisation zone. The polymerisation in the first polymerisation zone is conducted at a temperature within the range of from 50 to 115° C., preferably from 80 to 110° C. and in particular from 90 to 105° C. The pressure in the first polymerisation zone is from 1 to 300 bar, preferably from 5 to 100 bar.

The polymerisation in the first polymerisation zone may be conducted in slurry. Then the polymer particles formed in the polymerisation, together with the catalyst fragmented and dispersed within the particles, are suspended in the fluid hydrocarbon. The slurry is agitated to enable the transfer of reactants from the fluid into the particles.

The polymerisation usually takes place in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures. Preferably the diluent is a low-boiling hydrocarbon having from 1 to 4 carbon atoms or a mixture of such hydrocarbons. An especially preferred diluent is propane, possibly containing minor amount of methane, ethane and/or butane.

The ethylene content in the fluid phase of the slurry may be from 2 to about 50% by mole, preferably from about 2 to about 20% by mole and in particular from about 3 to about 15% by mole. The benefit of having a high ethylene concentration is that the productivity of the catalyst is increased but the drawback is that more ethylene then needs to be recycled than if the concentration was lower.

The slurry polymerisation may be conducted in any known reactor used for slurry polymerisation. Such reactors include a continuous stirred tank reactor and a loop reactor. It is especially preferred to conduct the polymerisation in loop reactor. In such reactors the slurry is circulated with a high velocity along a closed pipe by using a circulation pump. Loop reactors are generally known in the art and examples are given, for instance, in U.S. Pat. No. 4,582,816, U.S. Pat. No. 3,405,109, U.S. Pat. No. 3,324,093, EP-A-479186 and U.S. Pat. No. 5,391,654.

It is sometimes advantageous to conduct the slurry polymerisation above the critical temperature and pressure of the fluid mixture. Such operation is described in U.S. Pat. No. 5,391,654.

The amount of hydrogen is adjusted based on the desired melt flow rate and it also depends on the specific catalyst used. For many generally used Ziegler-Natta catalysts the molar ratio of hydrogen to ethylene is from 100 to 1500 mol/kmol, preferably from 200 to 1200 mol/kmol and in particular from 300 to 1000 mol/kmol.

The polymerisation in the first polymerisation zone may also be conducted in gas phase. A preferable embodiment of gas phase polymerisation reactor is a fluidised bed reactor. There the polymer particles formed in the polymerisation are suspended in upwards moving gas. The gas is introduced into the bottom part of the reactor. The upwards moving gas passes the fluidised bed wherein a part of the gas reacts in the presence of the catalyst and the unreacted gas is withdrawn from the top of the reactor. The gas is then compressed and cooled to remove the heat of polymerisation. To increase the cooling capacity it is sometimes desired to cool the recycle gas to a temperature where a part of the gas condenses. After cooling the recycle gas is reintroduced into the bottom of the reactor. Fluidised bed polymerisation reactors are disclosed, among others, in U.S. Pat. No. 4,994,534, U.S. Pat. No. 4,588,790, EP-A-699213, EP-A-628343, FI-A-921632, FI-A-935856, U.S. Pat. No. 4,877,587, FI-A-933073 and EP-A-75049.

In gas phase polymerisation using a Ziegler-Natta catalyst hydrogen is typically added in such amount that the ratio of hydrogen to ethylene is from 500 to 10000 mol/kmol, preferably from 1000 to 5000 mol/kmol to obtain the desired molecular weight of the low molecular weight ethylene homopolymer component.

The high molecular weight copolymer of ethylene and at least one alpha-olefin having 4 to 10 carbon atoms (B-1-2) is produced in the second polymerisation zone. Into the second polymerisation zone are introduced ethylene, alpha-olefin having 4 to 10 carbon atoms, hydrogen and optionally an inert diluent. The polymerisation in second polymerisation zone is conducted at a temperature within the range of from 50 to 100° C., preferably from 60 to 100° C. and in particular from 70 to 95° C. The pressure in the second polymerisation zone is from 1 to 300 bar, preferably from 5 to 100 bar.

The polymerisation in the second polymerisation zone may be conducted in slurry. The polymerisation may then be conducted along the lines as was discussed above for the first polymerisation zone.

The amount of hydrogen is adjusted based on the desired melt flow rate and it also depends on the specific catalyst used. For many generally used Ziegler-Natta catalysts the molar ratio of hydrogen to ethylene is from 0 to 50 mol/kmol, preferably from 10 to 35 mol/kmol.

Furthermore, the amount of alpha-olefin having from 4 to 10 carbon atoms is adjusted to reach the targeted density. The ratio of the alpha-olefin to ethylene is typically from 100 to 500 mol/kmol, preferably from 150 to 350 mol/kmol.

The polymerisation in the second polymerisation zone may also be conducted in gas phase. In gas phase polymerisation using a Ziegler-Natta catalyst hydrogen is typically added in such amount that the ratio of hydrogen to ethylene is from 5 to 500 mol/kmol, preferably from 30 to 150 mol/kmol to obtain the desired molecular weight of the high molecular weight ethylene copolymer component (B-1-2). The amount of alpha-olefin having from 4 to 10 carbon atoms is adjusted to reach the targeted density. The ratio of the alpha-olefin to ethylene is typically from 10 to 300 mol/kmol, preferably from 30 to 200 mol/kmol.

Coating Composition

The coating composition (B-2) comprises the multimodal ethylene copolymer (B-1) and eventual additives and other polymers. Preferably the coating composition (B-2) comprises from 80 to 100% by weight, more preferably from 85 to 100% by weight and in particular from 90 to 99% by weight of the multimodal ethylene copolymer (B-1).

In addition to the multimodal ethylene copolymer (B-1) the coating composition (B-2) typically contains conventional additives known in the art. Such additives are, among others, antioxidants, process stabilizers, UV-stabilizers, pigments and acid scavengers.

Suitable antioxidants and stabilizers are, for instance, 2,6-di-tert-butyl-p-cresol, tetrakis-[methylene-3-(3′,5-di-tert-butyl-4′hydroxyphenyppropionate]methane, octadecyl-3-3(3′5′-di-tert-butyl-4′-hydroxyphenyl)propionate, dilaurylthiodipropionate, distearylthiodipropionate, tris-(nonylphenyl)phosphate, distearyl-pentaerythritol-diphosphite and tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene-diphosphonite.

Some hindered phenols are sold under the trade names of Irganox 1076 and Irganox 1010. Commercially available blends of antioxidants and process stabilizers are also available, such as Irganox B225 marketed by Ciba-Geigy.

Suitable acid scavengers are, for instance, metal stearates, such as calcium stearate and zinc stearate. They are used in amounts generally known in the art, typically from 500 ppm to 10000 ppm and preferably from 500 to 5000 ppm.

Carbon black is a generally used pigment, which also acts as an UV-screener. Typically carbon black is used in an amount of from 0.5 to 5% by weight, preferably from 1.5 to 3.0% by weight. Preferably the carbon black is added as a masterbatch where it is premixed with a polymer, preferably high density polyethylene (HDPE), in a specific amount. Suitable masterbatches are, among others, HD4394, sold by Cabot Corporation, and PPM1805 by Poly Plast Muller. Also titanium oxide may be used as an UV-screener.

In addition the coating composition (B-2) may contain further polymers, such as carrier polymers used in additive masterbatches. The amount and nature of such polymers may be chosen freely within the limits discussed above as long as the properties of the coating composition are not negatively affected.

It is also possible to add a suitable amount of the adhesion polymer into the coating composition (B-2) to improve the adhesion between the pipe and the coating layer. In this way the amount of the polymer used in the adhesion layer may be reduced and in some cases it may be possible to eliminate the adhesion layer altogether.

Preferably, the coating composition (B-2) has a flow rate ratio FRR_(5/2) of from 2 to 10, preferably from 2 to 6 and in particular from 3 to 5. Preferably still, it has a flow rate ratio FRR_(21/5) of 15 to 40, more preferably from 20 to 35 and/or a shear thinning index SHI_(2.7/210) of from 35 to 100.

The coating composition (B-2) preferably has good mechanical properties. Thus, it has a high resistance to environmental stress cracking. Thus, preferably the coating composition (B-2) has a stress cracking resistance, as measured by CTL (Constant Tensile Load) at 60° C. and 5 MPa of at least 10 h, more preferably of at least 15 h.

Preferably the coating composition (B-2) has a wear index of at most 25, more preferably of at most 20.

Preferably the coating composition (B-2) has good performance at elevated temperatures. This is indicated by a high value of Vicat softening temperature, which preferably is at least 115° C., more preferably at least 116° C. and especially preferably at least 116.5° C. Furthermore, the coating composition (B-2) preferably has a Shore hardness of at least 57.

Especially preferably the coating composition (8-2) has a shear thinning index SHI_(2.7/210) of from 40 to 100 and the multimodal ethylene polymer (B-1) contained in the coating composition (B-2) has a value of Mw/Mn of from 24 to 50. Especially advantageously the composition (B-2) has a shear thinning index SHI_(2.7/210) of from 45 to 100 and the polymer (B-1) has the Mw/Mn of from 25 to 40.

Coating Layer

The coated pipe has a coating layer (B) which comprises the coating composition (B-2). The coating layer (B) comprises at least 75% by weight, preferably at least 80% by weight and more preferably at least 90% by weight of the coating composition (B-2), based on the total weight of the coating layer (B). Especially preferably, the coating layer (B) consists of the coating composition (B-2).

Pipe Coating and Coated Pipe

It is preferable to properly prepare the surface of the pipe before coating as it is known in the art. The pipe surface is typically inspected for any rust, dirt, flaws, discontinuities, and metal defects. All the excess material needs be removed from the pipe surface to make sure that the coating is properly adhered to the pipe. Suitable cleaning methods include air and water high pressure washing, grit or shot blasting and mechanical brushing. Also acid wash and chromate pre-treatment is sometimes used.

Typically the pipes are heated with induction heating up to about 200° C. The temperature is adjustable depending on the line speed and the material being used in the corrosion preventing layer (C). When the epoxy Teknos AR8434 is used the steel pipe is preferably heated to 190° C. The temperature decreases slightly during the coating process.

If epoxy powder (at 23° C.) is used it is typically sprayed on with epoxy guns, where the speed of the rotating pipe is about 9 m/min. The thickness of the epoxy and other coating materials are set in accordance with end use specified requirements. Normal thickness value for the epoxy layer (on-shore installations) is from 70 to 200 μm, such as 135 μm.

Materials that may be used in the corrosion protection layer (C) are, for instance, epoxy resins and organosilicon compounds. Examples of suitable epoxy resins are phenol-based epoxies and amine-based epoxies. These kinds of epoxies are sold, among others, under trade names of AR8434 (of Teknos), Scotchkote 226N (of 3M) and PE50-7191 (of BASF). Suitable organosilicon compounds have been disclosed in EP-A-1859926.

The extrusion of the adhesive (D) and the top-coating layer (B) may be performed, for instance, with two single screw extruders. They may have a diameter of, for instance, from 30 to 100 mm, such as 60 mm, and a length of from 15 to 50 L/D, such as 30 L/D. The temperature is typically controlled in several zones and the temperature of the PE adhesive (D) and coating (B) layer after the die is from 190 to 300° C., such as 225 and 250° C., respectively. Die widths are from 50 to 300 mm, such as 110 mm and 240 mm for the adhesive layer (D) and coating layer (B), respectively. Both adhesive (D) and the coating (B) layer are usually rolled tightly onto the pipe with a silicone pressure roller. The thickness of the adhesive layer (D) is typically from 200 to 400 μm, such as 290 μm. The thickness of the coating layer (B) is typically from 1 to 5 mm, preferably from 2 to 4 mm, such as 3.2 mm.

Materials suitable to be used in the adhesion layer are, for instance, acid or acid anhydride grafted olefin polymers, like polyethylene or polypropylene. Suitable polymers are, among others, fumaric acid modified polyethylene, fumaric acid anhydride modified polyethylene, maleic acid modified polyethylene, maleic acid anhydride modified polyethylene, fumaric acid modified polypropylene, fumaric acid anhydride modified polypropylene, maleic acid modified polypropylene and maleic acid anhydride modified polypropylene. Examples of especially suitable adhesion plastics are given in EP-A-1316598.

After the coating the coated pipe is cooled, for instance by providing water flow on the coated pipe surface.

The use of the coating composition (B-2) allows the coating process to be operated with a high throughput without operational problems, such as film line breaks. Moreover, the problem of neck-in variations after the die is reduced with the present coating compositions compared with the prior art compositions. Further still, smooth coatings having good mechanical properties are obtained.

EXAMPLES

Methods

CTL

CTL is determined by using a method similar to ISO 6252:1992 as follows.

The samples are prepared by pressing a plaque at 180° C. and 10 MPa pressure with a total length of 125 to 130 mm and a width at its ends of 21±0.5 mm. The plaque then is milled into the correct dimensions in a fixture on two of the sides with a centre distance of both holders of 90 mm and a hole diameter of 10 mm. The central part of the plaque has a parallel length of 30±0.5 mm, a width of 9±0.5 mm, and a thickness of 6±0.5 mm. A front notch of 2.5 mm depth is then cut into the sample with a razor blade fitted into a notching machine (PENT-NOTCHER, Norman Brown engineering), the notching speed is 0.2 mm/min. On the two remaining sides side grooves of 0.8 mm are cut which should be coplanar with the notch. After making the notches, the sample is conditioned in 23±1° C. and 50% relative humidity for at least 48 h. The samples are then mounted into a test chamber in which the active solution (10% solution of IGEPAL CO-730 in deionised water, chemical substance: 2-(4-nonyl-phenoxy)ethanol) is kept at 60° C. temperature. The samples are loaded with a dead weight corresponding to an initial stress of about 5 MPa and at the moment of breakage an automatic timer is shut off. The average of at least two measurements is reported.

The sample and the notch applied to the sample are shown in FIG. 1, in which:

A: total length of the specimen125 to 130 mm

B: distance between the centre points of the holders 90 mm

C: width of the specimen at the end 21±0.5 mm

D: hole diameter 10 mm

E: side grooves 0.8 mm

F: thickness of plaque 6±0.2 mm

G: width of narrow parallel part 9±0.5 mm

H: main notch 2.5±0.02 mm

The length of the narrow section of the specimen was 30±0.5 mm.

GPC

The weight average molecular weight Mw and the molecular weight distribution (MWD=Mw/Mn wherein Mn is the number average molecular weight and Mw is the weight average molecular weight) is measured by a method based on ISO 16014-4:2003 and ASTM D 6474-99. A Waters GPCV2000 instrument, equipped with refractive index detector and online viscosimeter was used with 2×GMHXL-HT and 1× G7000H columns from Tosoh Bioscience and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 140° C. and at a constant flow rate of 1 mL/min. 209.5 μL of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 15 narrow MWD polystyrene (PS) standards in the range of 1 kg/mol to 12 000 kg/mol. Mark Houwink constants were used for polystyrene and polyethylene (K: 19×10⁻³ mug and a: 0.655 for PS, and K: 39×10⁻³ mL/g and a: 0.725 for PE). All samples were prepared by dissolving 0.5-3.5 mg of polymer in 4 mL (at 140° C.) of stabilized TCB (same as mobile phase) and keeping for max. 3 hours at 160° C. with continuous shaking prior sampling in into the GPC instrument.

Melt Index, Melt Flow Rate, Flow Rate Ratio (MI, MFR, FRR):

Melt Index (MI) or Melt Flow Rate (MFR)

The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the melt viscosity of the polymer. The MFR is determined at 190° C. for PE. The load under which the melt flow rate is determined is usually indicated as a subscript, for instance MFR₂ is measured under 2.16 kg load, MFR₅ is measured under 5 kg load or MFR₂₁ is measured under 21.6 kg load.

Flow Rate Ratio (FRR)

The quantity FRR (flow rate ratio) is an indication of molecular weight distribution and denotes the ratio of flow rates at different loads. Thus, FRR_(21/2) denotes the value of MFR₂₁/MFR₂.

Neck-In

Neck-in was given as a width of the film after the 110 mm die in mm. In this test series neck-in is registered at the maximum peripheral speed of pipe the molten film can manage without variations in width. The neck-in was measured at a winding speeds of 15 and 20 RPM.

Peel Strength

Adhesion of polymer on steel was tested by Instron 1122 peel strength test equipment according to DIN 30670. A strip of 3 cm width is cut of the coating layer. The other end of the strip is fastened to pulling equipment and the pulling strength is measured during the peeling of the strip from the steel with a pulling speed of 10 mm/min. The results are expressed as N per cm. The peel strength was measured from the coatings produced at a screw speed of 50 RPM.

Pipe Coating

A steel pipe with a diameter of 114 mm was cleaned to remove the excess material from its surface. The pipe was then heated with induction heating to 190° C. Epoxy powder (Teknos AR8434) was then sprayed onto the pipe surface with the rotating speed of the line of 9 m/min so that the thickness of the epoxy layer was 135 μm. Then an adhesion plastic, a maleic acid anhydride grafted polyethylene adhesive, prepared according to composition 2 in EP 1 316 598 A1, was extruded onto the pipe by using a Barmag single screw extruder with an L/D ratio of 24 and a diameter of 45 mm and where the temperature of the melt after the die was 225° C. The die width was 110 mm. Simultaneously the composition of Example 1 was then extruded onto the adhesion layer by using a Krauss-Maffei extruder having a diameter of 45 mm and the UD ratio of 30. The die width was 240 mm and the temperature of the melt after the die was 250° C. The coating was conducted at extruder screw speeds of 25, 50 and 100 RPM. At the screw speed of 25 RPM five different winding speeds were run, namely 9, 15, 20, 25 and 30 RPM. The maximum throughput was measured at screw speed of 100 RPM.

Rheology

Rheological parameters such as Shear Thinning Index SHI and Viscosity were determined by using a Anton Paar Phisica MCR 300 Rheometer on compression moulded samples under nitrogen atmosphere at 190° C. using 25 mm diameter plates and plate and plate geometry with a 1.2 mm gap. The oscillatory shear experiments were done within the linear viscosity range of strain at frequencies from 0.05 to 300 rad/s (ISO 6721-1). Five measurement points per decade were made.

The values of storage modulus (G′), loss modulus (G″) complex modulus (G*) and complex viscosity (η*) were obtained as a function of frequency (ω). η₁₀₀ is used as abbreviation for the complex viscosity at the frequency of 100 rad/s.

Shear thinning index (SHI), which correlates with MWD and is independent of M_(W), was calculated according to Heino (“Rheological characterization of polyethylene fractions” Heino, E. L., Lehtinen, A., Tanner J., Seppälä, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1, 360-362, and “The influence of molecular structure on some rheological properties of polyethylene”, Heino, E. L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995.).

SHI value is obtained by calculating the complex viscosities at given values of complex modulus and calculating the ratio of the two viscosities. For example, using the values of complex modulus of 1 kPa and 100 kPa, then η*(1 kPa) and η*(100 kPa) are obtained at a constant value of complex modulus of 1 kPa and 100 kPa, respectively. The shear thinning index SHI_(1/100) is then defined as the ratio of the two viscosities η*(1 kPa) and η*(100 kPa), i.e. η(1)/η(100).

It is not always practical to measure the complex viscosity at a low value of the frequency directly. The value can be extrapolated by conducting the measurements down to the frequency of 0.126 rad/s, drawing the plot of complex viscosity vs. frequency in a logarithmic scale, drawing a best-fitting line through the five points corresponding to the lowest values of frequency and reading the viscosity value from this line.

Shore Hardness

Shore D hardness was determined according to ISO 868-2003. The measurement was done on round disks having a diameter of 35 mm and thickness of 4 mm and which were punched from compression moulded sheets having a thickness of 4 mm. The sheet was moulded according to ISO 1872-2 at 180° C. with a cooling rate 15° C./min. Finally, the plaques are conditioned at 23° C. at 50% relative humidity for at least two days.

Five measurements per sample are made. The measurement points are selected so that there is at least 10 mm distance to the edge of the disc and at least 6 mm distance to the nearest previous measurement point.

During the measurement a specified indenter (type D durometer) is forced into the test specimen under specified conditions (a mass of 5 kg). After 15 s the mass is removed, and the depth of penetration is measured.

Density

Density of the polymer was measured according to ISO 1183-2/1872-2B.

Comonomer Content:

13C-NMR analysis was used to determine the comonomer content of the samples. Samples were prepared by dissolving approximately 0.100 g of polymer and 2.5 ml of solvent in a 10 mm NMR tube. The solvent was a 90/10 mixture of 1,2,4-trichlorobenzene and benzene-d6. Samples were dissolved and homogenised by heating the tube and its contents at 150 C in a heating block.

The proton decoupled carbon-13 single pulse NMR spectra with NOE were recorded on a Joel ECX 400 MHz NMR spectrometer. The acquisition parameters used for the experiment included a flip-angle of 45 degrees, 4 dummy scans, 3000 transients and a 1.6 s acquisition time, a spectral width of 20 kHz, temperature of 125 C, WALTZ decoupling and a relaxation delay of 6.0 s. The processing parameters used included zero-filling to 32 k data points and apodisation using an exponential window function with in 1.0 Hz artificial line broadening followed by automatic zeroth and first order phase correction and automatic baseline correction.

Comonomer contents were calculated using integral ratios taken from the processed spectrum using the assignments described in J C. Randall's work (JMS—Rev. Macromol. Chem. Phys., C29(2&3), 201-317 (1989) using: E=(\alphaB+\alphaH+\betaB+\betaH+\gammaB+\gammaH+\delta++)/2 B=(methine B+2B+1B)/3 H=(methine H+4H+3H+2H)/4

where methine is the CH branch site, alpha, beta, gamma the carbon sits adjacent to the CH i.e. CH, alpha, beta, gamma, delta. \delta++ is the bulk CH2 site and the 1, 2, 3 and 4 sites representing the various carbon sites along the branch with the methyl group being designated 1. CE=100%*E/(E+B+H) CB=100%*B/(E+B+H) CH=100%*H/(E+B+H)

Example 1

A loop reactor having a volume of 50 dm³ was operated continuously at a temperature of 60° C. and a pressure of 62 bar. Into the reactor were introduced 42 kg/h of propane diluent, 2 kg/h of ethylene and 35 g/h of hydrogen. In addition 6.3 g/h of a solid polymerisation catalyst component sold by BASF under a trade name of Lynx 200 was introduced into the reactor together with triethylaluminium cocatalyst so that the ratio of aluminium to titanium was 30 mol/mol. The rate of polymer production was about 1.8 kg/h.

The slurry from the 50 dm³ loop reactor was withdrawn and transferred continuously to another loop reactor having a volume of 500 dm³ and which was operated at a temperature of 95° C. and a pressure of 60 bar. Into the reactor were introduced additional propane diluent, ethylene and hydrogen. The ethylene concentration in the fluid mixture was 3.4 mol-%, based on the total number of moles in the fluid mixture, and the rate of polymer production was about 32 kg/h. The conditions and data can be seen in Table 1.

The slurry from the loop reactor was withdrawn by using settling legs into a flash vessel operated at a temperature of 50° C. and a pressure of 3 bar where the hydrogen and major part of the hydrocarbons was removed from the polymer. The polymer was directed into a fluidised bed gas phase reactor operated at 85° C. temperature and 20 bar pressure. Into the reactor were introduced additional ethylene, 1-hexene comonomer, hydrogen and nitrogen as inert gas. Ethylene content in the fluidisation gas was 10 mol-%. The conditions and the data are shown in Table 1.

The resulting polymer powder was dried from hydrocarbons and mixed with 3000 ppm of Irganox B225, 1000 ppm of calcium stearate and 2.4% of carbon black, based on the final composition. The mixture was then extruded into pellets by using a CIM90P twin screw extruder (manufactured by Japan Steel Works). The properties of the compound are shown in Table 2.

The resulting composition was used in coating a steel pipe as described above in the description of the methods under the title “Pipe coating”. Data is shown in Table 2.

Examples 2 to 5 and Reference Examples 6R and 7R

The procedure of Example 1 was repeated except that conditions were as shown in Table 1. The compound data is shown in Table 2.

Reference Example 8R

The multimodal ethylene polymer was similar to Polyethene #3 of Example 2 of EP 837915.

TABLE 1 Polymerisation conditions Example 1 2 3 4 5 6R 7R 8R H₂/C₂ in loop, mol/kmol 722 752 745 745 757 564 536 MFR₂, loop, dg/min 770 800 815 815 575 300 280 384 Mw, loop, g/mol 25000 24000 22000 30000 30000 32000  21000 H₂/C₂ in gpr, mol/kmol 53 103 98 98 89 79  73 C₆/C₂ in gpr, mol/kmol 133 71 70 70 78 113   236¹⁾ Split, loop/gpr 49/51 51/49 51/49 51/49 51/49 45/55 45/55 45/55 MFR₂, g/10 min 0.61 0.52 0.58 0.61 0.54 0.51    0.57 MFR₅, g/10 min 2.7 2.3 2.5 2.6 2.4 2.0    2.2 Density, kg/m³ 941.1 949.7 950.0 949.9 948.4 941.3   940.3 941 Extruder throughput, kg/h 213 203 202 201 194 217 200 SEI, kWh/ton 146 169 174 152 148 168 166 Melt temperature, ° C. 217 226 226 222 223 224 230 Notes: ¹⁾1-butene as comonomer, C₄/C₂ - ratio

TABLE 2 Example 1 2 3 4 5 6R 7R 8R MFR₂, g/10 min 0.65 0.53 0.61 0.59 0.53 0.54 0.58 0.4 MFR₅, g/10 min 2.8 2.3 2.7 2.5 2.4 2.2 2.3 1.7 MFR₂₁, g/10 min 57 71 68 68 34 Density, kg/m³ 952.0 962.0 961.9 960.4 963.2 953.0 951.8 η_(0.05), Pa · s 22623 24412 22569 22721 25165 22999 21006 24267 η₃₀₀, Pa · s 495 543 524 519 525 603 616 682 SHI(2.7/210) 69.3 56.8 56.6 58.4 65.4 39.3 33.3 31.5 CTL, h 118 20 16 16 22 472 52 29 Vicat. ° C. 116.1 122.8 122.5 122.3 122.1 119.7 116.7 117.4 Shore hardness 58.2 61.7 61.0 61.2 60.7 58.9 58.3 58.1 Mw, g/mol 127000 134000 125000 140000 136000 115000 171000 Mn, g/mol 4280 4160 3600 3990 5400 5000 24700 Mw/Mn 29.6 32.3 34.7 35.1 25.2 22.9 6.9 Peel strength at 23° C. 385 279 322 411 393 581 556 585 Peel strength at 80° C. 208 193 161 185 168 236 232 191 Neck-in at 20 rpm, mm 84 80 83 83 85 80 78 76 Neck-in at 15 rpm, mm 98 93 98 96 94 89 87 90 Output, kg/h 78.3 78.9 83.8 83.1 79.2 72.6 71.9 72.6

It can be seen from the data that in Examples 1 to 5, having the production split within the scope of the present invention clearly had a higher output in the coating line, as well as a broader film after the die, than the Reference Examples 6R to 8R. 

The invention claimed is:
 1. A polymer coated pipe comprising a coating layer (B) covering said pipe, wherein the coating layer (B) comprises a coating composition (B-2) having a shear thinning index SHI_(2.7/210) of from 40 to 100, the SHI_(2.7/210) being determined from oscillatory shear experiments within the linear viscosity range of strain at frequencies from 0.05 to 300 rad/s according to ISO 6721-1 as the ratio of the complex viscosities η (2.7 kPa)/η (210 kPa), wherein the coating composition (B-2) comprises a multimodal ethylene copolymer (B-1), which is a copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms, wherein the multimodal ethylene copolymer (B-1) further comprises: (B-1-1) from 49 to 59% based on the weight of the multimodal ethylene copolymer (B-1) a low molecular weight ethylene homopolymer component, said low molecular weight ethylene homopolymer component (B-1-1) having a weight average molecular weight of from 5000 g/mol to 70000 g/mol; and (B-1-2) from 51 to 41% based on the weight of the multimodal ethylene copolymer (B-1) a high molecular weight ethylene copolymer component, said high molecular weight ethylene copolymer component (B-1-2) having a weight average molecular weight of from 100000 g/mol to 700000 g/mol; and the multimodal ethylene copolymer (B-1) has: a weight average molecular weight of from 70000 g/mol to 250000 g/mol; and a melt index MFR₂, determined according to ISO 1133 at 190° C. under a load of 2.16 kg, of from 0.05 g/10 min to 5 g/10 min; and a melt index MFR₅, determined according to ISO 1133 at 190° C. under a load of 5 kg, of from 1.0 to 10 g/10 min; and a density of from 930 kg/m³ to 955 kg/m³; and a ratio of the weight average molecular weight to the number average molecular weight M_(w)/M_(n) of from 24 to 50; and wherein the coating composition (B-2) has a Shore hardness of at least
 57. 2. The pipe according to claim 1 wherein the multimodal ethylene copolymer (B-1) has a density of 935 to 955 kg/m³.
 3. The pipe according to claim 1 wherein the coating composition (B-2) has a melt index MFR₂, determined according to ISO 1133 at 190° C. under a load of 2.16 kg, of 0.1 to 1.2 g/10 min and MFR₅, determined according to ISO 1133 at 190° C. under a load of 5 kg, of 1.0 to 5.0 g/10 min.
 4. The pipe according to claim 1 wherein the multimodal ethylene copolymer (B-1) and the high molecular weight ethylene copolymer component (B-1-2) are copolymers of ethylene and one or more alpha-olefins having from 6 to 10 carbon atoms.
 5. The pipe according to claim 1 wherein the pipe is a metal pipe.
 6. The pipe according to claim 1 wherein the pipe is covered by a corrosion preventing layer (C) which is further covered by the coating layer (B).
 7. The pipe according to claim 6 wherein the corrosion preventing layer (C) is covered by an adhesive layer (D), which is further covered by the coating layer (B).
 8. The pipe according to claim 1 wherein the pipe is covered by an adhesive layer (D), which is further covered by the coating layer (B).
 9. The pipe according to claim 1 wherein the coating layer (B) comprises from 75 to 100% by weight based on the total weight of the coating layer (B) of the coating composition (B-2).
 10. The pipe according to claim 1 wherein the coating composition (B-2) comprises from 80 to 100% by weight, based on the total weight of the coating composition (B-2), of the multimodal ethylene copolymer (B-1).
 11. The pipe according to claim 1 wherein the coating composition (B-2) has an SHI_(2.7/210) of from 45 to
 100. 12. The pipe according to claim 1 wherein the multimodal ethylene copolymer (B-1) has a ratio of weight average molecular weight to number average molecular weight, M_(w)/M_(n) of from 25 to
 40. 13. The pipe according to claim 1, produced by a process comprising the steps of: providing a pipe; applying a coating layer (B) onto the pipe, wherein the coating layer (B) comprises a coating composition (B-2) having a shear thinning index SHI_(2.7/210) of from 40 to 100, the SHI_(2.7/210) being determined from oscillatory shear experiments within the linear viscosity range of strain at frequencies from 0.05 to 300 rad/s according to ISO 6721-1 as the ratio of the complex viscosities η (2.7 kPa)/q (210 kPa), wherein the coating composition (B-2) comprises a multimodal ethylene copolymer (B-1), which is a copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms, wherein the multimodal ethylene copolymer (B-1) further comprises: (B-1-1) from 49 to 59% based on the weight of the multimodal ethylene copolymer (B-1) a low molecular weight ethylene homopolymer component, said low molecular weight ethylene homopolymer component (B-1-1) having a weight average molecular weight of from 5000 g/mol to 70000 g/mol; and (B-1-2) from 51 to 41% based on the weight of the multimodal ethylene copolymer (B-1) a high molecular weight ethylene copolymer component, said high molecular weight ethylene copolymer component (B-1-2) having a weight average molecular weight of from 100000 g/mol to 700000 g/mol; and the multimodal ethylene copolymer (B-1) has a weight average molecular weight of from 70000 g/mol to 250000 g/mol; and a melt index MFR₂, determined according to ISO 1133 at 190° C. under a load of 2.16 kg, of from 0.05 g/10 min to 5 g/10 min; and a melt index MFR₅, determined according to ISO 1133 at 190° C. under a load of 5 kg, of from 1.0 to 10 g/10 min; and a density of from 930 kg/m³ to 955 kg/m³; and a ratio of the weight average molecular weight to the number average molecular weight M_(w)/M_(n) of from 24 to 50; and wherein the coating composition (B-2) has a Shore hardness of at least
 57. 14. The pipe according according to claim 13, the process further comprising the steps of: (i) polymerizing, in a first polymerization stage, said low molecular weight ethylene homopolymer component (B-1-1) in the presence of a polymerization catalyst, hydrogen, ethylene and optionally an inert diluent to produce an ethylene homopolymer having a weight average molecular weight of from 5000 g/mol to 70000 g/mol which constitutes from 49 to 59% by weight of the multimodal ethylene copolymer (B-1); and (ii) polymerizing, in a second polymerization stage, said high molecular weight ethylene copolymer component (B-1-2), which is a copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms, in the presence of a polymerization catalyst, ethylene, at least one alpha-olefin comonomer having from 4 to 10 carbon atoms, and optionally hydrogen and/or an inert diluent to produce a copolymer of ethylene and one or more alpha-olefin comonomers having from 4 to 10 carbon atoms having a weight average molecular weight of from 200000 g/mol to 700000 g/mol, which high molecular weight ethylene copolymer component (B-1-2) constitutes from 41 to 51% by weight of the multimodal ethylene copolymer (B-1); and wherein said first and said second polymerization step are performed as successive polymerization steps with the polymer product produced in any previous step being present in the subsequent step(s) and wherein said first step and said second step can be performed in any order; (iii) recovering said multimodal ethylene copolymer (B-1); (iv) obtaining the coating composition (B-2) comprising 80 to 100% by weight, of the multimodal ethylene copolymer (B-1), optional additives and optional other polymers; (v) applying said coating composition (B-2) onto the pipe to form the coating layer (B).
 15. The pipe according to claim 14 wherein the polymerization step (i) is performed in a polymerization stage preceding the polymerization step (ii).
 16. The pipe according to claim 14 wherein the polymerization step (ii) is performed in a polymerization stage preceding the polymerization step (i).
 17. The pipe according to claim 14 wherein the polymerization is conducted in the presence of a polymerization catalyst together with an aluminium alkyl cocatalyst, wherein said polymerization catalyst comprises a solid component comprising titanium, halogen and magnesium, optionally supported on a particulate support.
 18. The pipe according to claim 17 wherein the solid catalyst component is introduced into the first polymerization step and is therefrom transferred into the subsequent step(s) and where no additional solid catalyst component is introduced into said subsequent step(s).
 19. The pipe according to claim 18 wherein the catalyst comprises a titanium compound and a magnesium halide without an inert inorganic oxide support.
 20. The pipe according to claim 13 wherein a corrosion preventing layer (C) is applied onto the pipe before coating it with the coating layer (B).
 21. The pipe according to claim 20 wherein an adhesive layer (D) is applied onto the corrosion preventing layer (C) before coating it with the coating layer (B).
 22. The pipe according to claim 13, wherein an adhesive layer (D) is applied onto the pipe before coating it with the coating layer (B).
 23. The pipe according to claim 13 wherein the multimodal ethylene copolymer (B-1) has a ratio of weight average molecular weight to number average molecular weight, M_(w)/M_(n) of from 25 to
 40. 24. The pipe according to claim 13 wherein the multimodal ethylene copolymer (B-1) has a density of from 935 to 955 kg/m³.
 25. The pipe according to claim 13 wherein the coating composition (B-2) has an SHI_(2.7/210) of from 45 to
 100. 26. The pipe according to claim 3 wherein the coating composition (B-2) has a melt index MFR₂, determined according to ISO 1133 at 190° C. under a load of 2.16 kg, from 0.2 to 1.0 g/10 min. 